CN101563374B - Phase separator and monomer recycle for supercritical polymerization process - Google Patents

Abstract

This invention relates to a process for polymerizing olefins, comprising the steps of: (a) contacting in one or more reactors, in a dense fluid homogeneous polymerization system, olefin monomers having three or more carbon atoms present at 30 weight % or more (based upon the weight of the monomers and comonomers entering the reactor), with: 1) one or more catalyst compounds, 2) one or more activators, 3) from 0 to 50 mole % comonomer (based upon the amount of the monomers and comonomers entering the reactor), and 4) 0 to 40 wt % diluent or solvent (based upon the weight of the polymerization system), at a temperature above the crystallization temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point pressure of the polymerization system and less than 200 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, any scavenger present, and the polymer product; (b) forming a reactor effluentcomprising a polymer-monomer mixture; (c) optionally heating the polymer-monomer mixture of (b) after it exits the reactor and before or after the pressure is reduced in step (e); (d) collecting the polymer-monomer mixture of (b) in a separation vessel; (e) reducing the pressure of the reactor effluent comprising the polymer-monomer mixture of (b) below the cloud point pressure to form a two-phase mixture comprising a polymer-rich phase and a monomer rich phase either before or after collecting the polymer-monomer mixture in the separation vessel where the pressure in the reactor (or at leastone reactor if more than one is in use) is between 7 and 100 MPa higher than the pressure in the separation vessel and the temperature in the separation vessel is above the crystallization temperatur e of the polymer or above 80 DEG C if the polymer has no crystallization temperature, whichever is higher; (f) separating the monomer-rich phase from the polymer-rich phase.

Description

Be used for the phase separator and the monomer recycling of supercritical polymerization process

Contriver: Chris Friedersdorf, Patrick Brant and Gabor Kiss

The right of priority that requires

11/854,936 the right of priority that the application has required to propose on September 13rd, 2007, it is the USSN 11/714 that submitted on March 6th, 2007; 546 part continues; The right of priority of the USSN 60/876,193 that this USSN 11/714,546 has required to submit on December 20th, 2006 is also benefited from it.The application has also required the USSN60/905 of submission on March 6th, 2007, and 247 right of priority is also benefited from it.

Technical field

The present invention relates to polymerization of olefin monomers under super critical condition, wherein principal monomer has three or more a plurality of carbon atom.Special, the present invention relates to the lower-molecular-weight component of polymerization system is separated with polymerisate, and lower-molecular-weight component is recycled in the polymerization system.

Background technology

Since 1980 mid-nineties 90s; Metalloscene catalyst is used for mainly being used for preparing the high-pressure reactor of ethene trunk polymer (therein ethylene is the polyolefine of principal monomer); Comprise the ethylene copolymer with comonomer, this comonomer is one or more in propylene, butylene and the hexene, and other certain monomers; 4-methyl isophthalic acid for example, the 5-hexadiene.For example, people's such as Langhausen U.S. patent No.5,756,608 have reported a kind of use bridged metallocents polymerization catalyst C ₂To C ₁₀The method of 1-alkene.Up to date; The preparation Vestolen PP 7052 is counted as unpractically and irrealizable under the homogeneous phase super critical condition, can prepare commercial useful polyacrylic catalyst system because lack being higher than critical temperature and being higher than under a lot of temperature of solid-fluid phase transition temperature.But; WO2004/026921 disclose a kind of in high pressure system the method for the commercial useful Vestolen PP 7052 of preparation (and other relevant polymkeric substance), the advantage that this method provides is, has for example increased the throughput of catalyzer; High-throughput, the short residence time etc.Same, the new acrylic polymer with design composition and/or MWD is also disclosed.Therefore present technical need exploitation new can be very economical and efficient with the lower-molecular-weight component of polymerization process and the isolating method of polymkeric substance in this novel method, and be preferably can be with the method in the polymerization system charging that is recycled to of those lower-molecular-weight component economy.

WO 1993/11171 discloses a kind of process for preparing polyolefins, and it comprises successive feed olefin monomer and metallocene catalyst system in reactor drum.The polymerization of monomer successive is to provide monomer-polymeric blends.Reaction conditions remains below this mixture under the pressure of cloud point pressure of system, and therefore form by the phase that is rich in polymkeric substance be rich in the two-phase reaction mixture of monomeric phase composite.Temperature of reaction also remains on the fusing point that is higher than polymkeric substance.

WO 1992/14766 discloses a kind of method, and the step that this method comprises has (a) successive feed olefin monomer and the catalyst system with metallocene components and cocatalyst component in reactor drum; (b) under elevated pressure in the polymeric area reactor drum successive polymerization single polymerization monomer; (c) successive is removed polymer/monomer mixture from reactor drum; (d) successive separating monomer from the fused polymkeric substance; (e) reducing pressure is rich in monomeric phase and is rich in polymkeric substance mutually with formation; And (f) separating monomer from reactor drum.WO 1992/14766 concentrates on the catalyst deactivation system of the polymkeric substance that is used to be rich in ethene; But openly be not used to prepare the single-phase polymerizing condition of commercial useful acrylic polymer, how also not having to describe under super critical condition is separated through the acrylic polymer fluid-liquid obtains the economic interests of lower power intake and low plant investment.

WO2004/026921 discloses a kind of under the temperature of the Tc that is higher than polymerization system and be lower than the alkene scope that polymerization under the pressure that the polymerization system cloud point is not less than 10MPa has three or more a plurality of carbon atoms; And optional alkene and/or diolefine comonomer widely; And catalyst compound (for example metallocenes); Acvator and the thinner of choosing wantonly or the method for solvent, wherein polymerization system comprises the comonomer of any existence, the thinner of any existence or solvent; Polymeric articles, the alkene that wherein has three or more a plurality of carbon atoms exists with 40 weight % or more amount.Therefore; WO2004/026921 has instructed the polymerization method that under supercritical operation condition widely, is used to prepare the commercial useful polymkeric substance that is rich in propylene (perhaps being rich in higher terminal olefin); Comprise single-phase and two-phase reaction system; Use or do not use the inert solvent component, wherein polymkeric substance in solution, promptly its be dissolved in the homogeneous reaction medium or mainly be dissolved in the two-phase system biphase one mutually in.This invention has been introduced and a kind ofly has been used for that the effective and economic lower-molecular-weight component with reaction medium separates with polymkeric substance and with the method that is recycled to the polymerization system material of lower-molecular-weight component economy, it is useful in the description of WO2004/026921 in polymerization system.

U.S.6,881,800, US 7,163,989 and WO2002/034795 (Friedersdorf) a kind of polymerization system that is widely used in multiple polyolefin polymer has been described, comprise the polymkeric substance that is rich in propylene, and metallocene catalyst system.But because the system of describing is the solvent based system, disclosed polymerization system pressure range is 7.5 to 20MPa, and it is lower than the scope among the present invention (20 to 200MPa).

Although technical these progress; Also exist and be used to provide the commercial useful polymkeric substance that is rich in propylene; Particularly those have the needs of polymerization method of the polymkeric substance of HMW and high-crystallinity, under higher temperature of the method more possible than other and yield-power, prepare them, and separating monomer economic from polymkeric substance is provided; Promptly have low capital investment and low energy expenditure, therefore the advantage of product separation and monomer recycling is provided.

Summary of the invention

The present invention relates to a kind of method of olefin polymerization; Comprise the steps: that (a) is in dense thick fluid polymerization in homogeneous phase system; In one or more reactor drums; Under the temperature that is higher than the polymerization system Tc and be not less than under following 10MPa of polymerization system cloud point pressure (preferred 1MPa) and the pressure, make olefinic monomer and 1 with three or more a plurality of carbon atoms in 30 weight % or more amount (based on the monomer that gets into reactor drum and the weight of comonomer) existence less than 200MPa) one or more catalyst compound, 2) one or more acvators; 3) comonomer of 0 to 50 mole of % (based on the monomer that gets into reactor drum and the amount meter of comonomer); And 4) 0 to 40wt% thinner or solvent (based on the weight meter of polymerization system) contact, wherein polymerization system comprises monomer, the comonomer of any existence; The thinner of any existence or solvent, the scavenging agent of any existence and polymeric articles; (b) form the reactor effluent that comprises polymkeric substance-monomer mixture; (c) after it leaves reactor drum and in step (e), reduce the polymkeric substance-monomer mixture of optionally heating (b) before or after the pressure; (d) polymkeric substance-monomer mixture of collection (b) in separation vessel; (e) pressure that comprises the reactor effluent of polymkeric substance-monomer mixture in (b) is reduced to below the cloud point pressure so that in separation vessel, form before or after collected polymer-monomer mixture and comprises the phase that is rich in polymkeric substance and be rich in monomeric two-phase mixture mutually; Wherein reactor drum (if use more than a reactor drum then be at least one reactor drum) if in pressure 7 and the 100MPa of pressure in being higher than separation vessel between and the Tc or the polymkeric substance that are higher than polymkeric substance of the temperature in the separation vessel when not having Tc; This temperature is higher than 80 ℃, and whichever is higher; (f) will be rich in polymkeric substance be rich in monomeric being separated; (g) be rich in the monomeric one or more reactor drums that are recycled to mutually in (a) isolating; And (h) from be rich in polymkeric substance mutually reclaim polymkeric substance.

Description of drawings

Fig. 1 representes the pattern description of binode and spinodal border thermodynamic definitions.

Fig. 2 representes the phasor of the typical polymerisation medium of the present invention.

Fig. 3 representes Polymer Achieve ^TM1635 cloud point thermo-isopleth.(Achieve1635 is by ExxonMobil Chemical Company, Houston, Texas be purchased acquisition metallocene catalyst have a 32g/10min melt flow index (I ₁₀/ I ₂1238,190 ℃ of-ASTM, isotactic polyprophlene 2.16kg)).

Fig. 4 has shown that the mixture by isotactic polyprophlene (isotaxy PP) and propylene monomer forms be rich in monomeric mutually with the density mutually that is rich in polymkeric substance.

Fig. 5 the present invention includes the chart of the polymerization method of phase separator for basis.

Detailed Description Of The Invention

For the purpose of the present invention and claim, catalyst system is defined as combining of one or more catalyst precursor compounds and one or more acvators and any optional coactivator.Any part of catalyst system can be optionally supported on solid particulate, and carrier also is the part of catalyst system in this situation.

The critical properties of pure substance and mixture

Pure substance comprises that all types of hydrocarbon can exist with subcritical or supercritical state, and this depends on their temperature and pressure.The material that is in their supercritical staties has the interesting physics and the thermodynamic property of exploitation in the present invention.Most particularly, because supercutical fluid has stood big variation under pressure, their density and the dissolving power of polymkeric substance changed in the scope widely.Want to be in supercritical state, material must have the temperature and the pressure that is higher than its emergent pressure (Pc) of the critical temperature (Tc) that is higher than it.The mixture of hydrocarbon; The mixture that comprises monomer, polymkeric substance and optional solvent; Have pseudocritical temperature (Tc) and pseudocritical pressure (Pc), it all is to estimate through the mole-mark-weighed average of the corresponding critical properties of the component of mixture (Tc or Pc) for many systems.The mixture that the pseudocritical temperature that temperature is higher than they and pressure are higher than their pseudocritical pressure is called and is in supercritical state or mutually, and the thermodynamic behavior of supercritical mixtures will be similar to overcritical pure substance.Based on the object of the invention, the critical temperature (Tc) of some pure substance relevant and emergent pressure (Pc) with the present invention be those at Handbook of Chemistry andPhysics, David R.Lide chief editor; The 82nd edition, 2001-2002, CRC Press; LLC. New York is found in 2001.Special, the Tc of the material of selection and Pc are:

Title	Tc (K)	Pc (MPa)	Title	Tc (K)	Pc (MPa)
						Hexane	507.6	3.025	Propane	369.8	4.248
Trimethylmethane	407.8	3.64	Toluene	591.8	4.11
						Ethane	305.3	4.872	Methane	190.56	4.599
Tetramethylene	460.0	4.98	Butane	425.12	3.796
						Pentamethylene	511.7	4.51	Ethene	282.34	5.041
1-butylene	419.5	4.02	Propylene	364.9	4.6
						The 1-amylene	464.8	3.56	Cyclopentenes	506.5	4.8
Pentane	469.7	3.37	Different propane	460.4	3.38
						Benzene	562.05	4.895	Hexanaphthene	553.8	4.08
The 1-hexene	504.0	3.21	Heptane	540.2	2.74

273.2K＝0℃。Phase behavior

Hydrocarbon phase or hydrocarbon mixture phase; Polymerization system for example; Or the phase that is rich in polymkeric substance that forms by the polymerization system in the separator of one or more open methods or be rich in monomeric phase, perhaps any other comprises that monomer and mixture of polymers are the thermodynamic properties of key.Mixture can be solid, steam, liquid or supercutical fluid mutually.Based on this purpose, supercutical fluid can simply refer to the fluid phase mutually sometimes.When the pressure that surpasses critical temperature or pseudocritical temperature and mixture when the temperature of mixture surpasses its emergent pressure or pseudocritical pressure, just it is confirmed as the supercutical fluid phase.

When mixture relies on the change that changes temperature, pressure and/or composition and the phase time that changes them, they are called pass the phase border, this can be expressed as track (curve) a little on temperature and pressure figure, and wherein said curve is applied to the mixture of given composition.Based on the object of the invention, the phase border between fluid and the liquid phase will be called fluid-liquid phase border, and the transformation of passing the temperature and pressure on these borders can be called fluid-liquid and changes.Based on the object of the invention, the phase border between single uniform fluid and two fluids (fluid-fluid) phase will be expressed as cloud point curve.Because uniformly separately fluid (liquid state or supercutical fluid) mixture passes cloud point, it change into different densities and composition two mutually.The cloud point pressure of naming a person for a particular job and referring to it that on cloud point curve, provides.Under given temperature; Cloud point pressure can measuring for this pressure under or be lower than the pressure that polymerization system under this pressure becomes muddiness, as J.VladimirOliveira, C.Dariva and J.C.Pinto; Described in the Ind.Eng, Chem.Res.29 (2000) 4627.For the purpose of the present invention and claim, adopting lasing fluorescence and measuring cloud point to the pressure under the fixed temperature through the polymerization system of selecting on the sensitive cell at the opening entry that scattering of light increases fast in the cloud point chamber.Description-based purpose, Fig. 2 described the typical polymerization medium cloud point curve (1 the crust=100kPa).

Phase border between solid and the fluid (being between solid and the liquid or between solid and the supercutical fluid) will be expressed as solid-fluid (perhaps solid-liquid, when fluid is liquid mutually) phase border.Pass solid-fluid (or solid-liquid) phase border and will be expressed as solid-fluid (or solid-liquid) transformation.Independent point can be called solid-fluid (or solid-liquid) transition temperature on solid-fluid (or solid-liquid) phase border.But two different solid-fluids of many mixtures performance place (or solid-liquid) phase border of indication in the present disclosure, this depends on the direction of phase change.One is fusing; Promptly when the direction of phase change be (one or more liquid state or supercutical fluid phase) and when not having solid from solid or from solid-fluid mixture to the fluid phase; Another is crystallization, promptly when the direction of phase change for never containing solid fluid (one or more liquid state or supercutical fluid) mutually when containing the phase of solid phase.When needs are distinguished this transformation of two types, will use fusing and crystallization one speech, and the mutually borderline temperature of fusion that refers to it or its Tc of naming a person for a particular job separately.Purpose for the present invention and claim; On sensitive cell, adopt the helium lasing fluorescence in the cloud point chamber through the polymerisation medium of selecting, and beginning that increases fast in the scattering of light that indication solid phase (crystallization) forms or record temperature (under given pressure) and mensuration solid-fluid (or solid-liquid) changes with fluid-solid (or liquid-solid) mutually when the beginning that the scattering of light of indication solid phase disappeared (fusing) reduces fast.Description-based purpose, Fig. 2 has described the crystallization of typical polymerization medium and the solid-fluid of fusing-type (solid-supercutical fluid or solid-liquid) border mutually.

Phase density

As top described; The measurement on phase border is used J.Vladimir Oliveira through the mixture to given composition under a plurality of temperature; C.Dariva and J.C.Pinto; Ind.Eng, the experimental technique of describing among the Chem.Res.29 (2000) 4627 carries out a plurality of cloud point pressure surveys and measures.This phase data boundary is used for substitution state equation (EOS) pattern with the single phase of prediction in a temperature and pressure scope, i.e. fluid, liquid, the thermodynamics of solid and/or steam and physical properties.For supporting cut-and-try work of the present invention, relevant channel theory (SAFT) the EOS version (Ind.&Eng.Chem.Res.37 (1998) 4453 for H.Adidharma, M.Radosz) of statistics that will be called SAFT1 is used for this purpose.Experiment is carried out under high temperature and high pressure owing to be separated; Usually to take a sample with composition or the physical properties of measuring them mutually be unpractical to single in multiphase mixture, so the character of the prediction of these phases is used to replace under support of the present invention the directly value of measurement.This method is confirmed in other instances, and wherein the material balance from pilot plant and commercial plant is used to confirm SAFT1 EOS prediction.As an instance, US 6,881; 800 with US 7,163,989 in the polymerization system described and the SAFT1 EOS pattern of liquid-liquid separation system; It comprises and some similar polymerization thing of the present invention, monomer and catalyzer; But they comprise a large amount of relatively alkane solvents in polymerisation medium, and being lower than operation under the pressure of the present invention, identify through the type of these material balance.

Spinodal decomposes

Mixture, for example the phase border of polymerisation medium can be described as temperature and pressure (T, P) figure of constant group resulting mixture; As shown in Figure 2; Perhaps optionally, they can be described as the T of mixture under the constant pressure, c figure (as among Fig. 1 through the binodal curve conceptual illustration) or steady temperature under the P of mixture; C figure, wherein symbol c is used for the expression composition.For multi-component mixture, it is formed through a series of composition variable c _iMark, wherein i refers to each component in the mixture, but for two-component mixture, will form with single argument c mark fully.Usually; Polymerisation medium of the present invention is a multicomponent mixture; But for the object of the invention is described, be that the two-component mixture of polymkeric substance and independent low molecular weight hydrocarbon does not have general omission through considering polymerisation medium, and composition variable c can be used for representing the concentration of polymkeric substance.As an example; If we use T, the phase border under the c mark constant P, as shown in Figure 1; Fluid-liquid phase border occurs as curve that (following general designation is used for the term of technology then; We specify it is binodal curve), wherein the concentration at the minimum value of temperature (it also is called than lower critical solution temperature usually, or LCST) place is called critical polymer concentration (c _Crit).The binodal curve on this expression two phases (fluid-liquid) phase border is the track of point, wherein single-phase polymerisation medium be rich in monomeric mutually and the two-phase mixture that is rich in the phase of polymkeric substance balance each other.Can know obviously that from Fig. 1 for any given temperature and pressure, it uses T ₁Place's sea line is represented, has two and polymerisation medium equilibrated mixture composition, and so their mutual each other balances.A kind of for being rich in monomeric component in these blend compositions, another kind of (these two components are labeled as c ' and c ") on Fig. 1 for the component that is rich in polymkeric substance.The base section of Fig. 1 has been explained expression two-component mixture partial potential (Δ μ ₁) as equaling T in temperature ₁The time (noticing that every other T value all can make up similar curve) c the curve of function.Be also noted that Δ μ ₁(c ')=Δ μ ₁(c ") is because for two kinds of mixtures of equilibrated, their partial potential must equate.Other c values are following on the curve, Δ μ ₁Be assumed to other value because these other components not with c ' and c " balance.Along this Δ μ ₁Curve has two special points, wherein Δ μ ₁First partial derivative about forming is 0 $(\∂\mathrm{\Δ}{\mathrm{\μ}}_1/\∂c=0).$ As among Fig. 1 through graphical configuration explanation, this is the thermodynamics threshold value on definition spinodal border.For on the spinodal border or composition wherein; It is very different from balance forming unsettled two-phase mixture on the thermodynamics to be rich in the composition of monomer and the phase that is rich in polymkeric substance, and it tends to form the form that the successive of common successive form rather than two in mutually is dispersed in other droplets in mutually.In the zone that Fig. 1 cross-hatched is drawn, mixture tends to form wherein two forms that are dispersed in another phase continuum in mutually.The concentration of polymkeric substance is higher than c in polymerisation medium _CritThe time, what be rich in polymkeric substance is successive mutually, and the concentration of polymkeric substance is lower than c in polymerisation medium _CritThe time, being rich in monomeric is successive mutually.In many embodiments of the present invention, polymerisation medium is a monophasic fluid, to such an extent as to (T, P c) place it in the single phase region outside the binode border on Fig. 1 to its thermodynamic state.The spinodal decomposition course refers to the quick change that causes temperature and pressure moves through border inboard point up to the spinodal border of binode and spinodal with the thermodynamic state with system process.In order to make this variation is effectively in the common continuous morphology that produces expectation, binode with spinodal border (zone that Fig. 1 cross-hatched is drawn) to such an extent as between the zone in residence time of system thermodynamic state enough lack the form of not expecting and do not have time enough to establish.The exact value that for each polymerisation medium, satisfies the time of this threshold value must experimental mensuration.The spinodal border can also be depicted at constant to be formed on the phasor of overdraft to the curve of temperature, as shown in Figure 2.Can be at paper " ALow-Energy Solvent Separation Method ", T.G.Gutowski etc., PolymerEngineering and Science, March 1983, v.23, find the complete of this notion to touch upon among the No.4.

Term " is rich in monomeric phase " or " being rich in monomeric logistics " is defined as during the course expression and concentrated monomeric phase or the logistics that is present in upper reaches logistics or the equipment.For example in the phase separator of the disclosure of invention, be rich in the monomeric monomer that is present in reactor drum or its elute that concentrated mutually.Leave the monomeric monomer that comprises than is present in the monomer greater concn in the reactor effluent mutually of being rich in of present disclosure phase separator.Special, be rich in monomer concentration in the elute that monomeric logistics has than is present in reactor exit 10% the unreacted monomer of Duo at least and exist, preferably many at least 20%, preferably many at least 30%, preferably many at least 40%, preferably much more at least 50%.Similarly, " be rich in the phase of polymkeric substance " or " being rich in the logistics of polymkeric substance " is defined as during the course expression and concentrated phase or the logistics that is present in the polymkeric substance in upper reaches logistics or the equipment.For example in the phase separator of the disclosure of invention be rich in polymkeric substance concentrated the monomer that is present in reactor drum or the reactor effluent mutually.Leave the monomer of greater concn in the elute that the monomeric logistics of being rich in of present disclosure phase separator comprises than is present in it.Special, the concentration that the logistics that is rich in polymkeric substance has than is present in a polymkeric substance in the elute of reactor exit Duo 10% at least, and is preferably many at least 20%, preferably many at least 30%, preferably many at least 40%, and preferably much more at least 50%.Fig. 4 of present disclosure further illustrate be rich in monomer be rich in polymkeric substance mutually with the implication of logistics.

Polymerization system

High alpha-olefin or high alpha-olefin are defined as the terminal olefin with four or more a plurality of carbon atoms.

The polymerization of definition comprises any polyreaction, for example equal polymerization and copolymerization.

Copolymerization is defined as and comprises any two or more monomeric polyreactions.

When the polymkeric substance of mentioning relates to when comprising alkene, the alkene that is present in the polymkeric substance is the polymerized form of alkene.

Catalyst system is defined as the combination of one or more catalyst precursor compounds (also being called catalyzer or catalyst compound) and one or more acvators.Any part of catalyst system can be optionally supported on solid particulate, and carrier also is the part of catalyst system in this situation.

Polymerization system is defined as and comprises that monomer adds comonomer addition polymerization compound and adds the reaction system that optional inert solvent/thinner adds optional scavenging agent.It should be noted that for ease with clear for the purpose of, catalyst system always is independent of other components that are present in the reaction system and calls in this detailed description.In this, here the polymerization system of definition than technical by convention think that typically catalyst system is narrow as the polymerization of a reaction system part.In this definition, the mixture that is present in reactor drum and its elute is made up of polymerization system and catalyst system.

Polymerisation medium is defined as the elute mixture from polymerization system, comprises that unreacted monomer adds comonomer addition polymerization compound and adds optional inert solvent/thinner and add catalyst residues and add optional scavenging agent.Except as otherwise noted, the temperature and pressure of polymerisation medium hypothesis equals the temperature and pressure of polymerization system.

Based on the object of the invention, solvent and the interchangeable use of thinner one speech, and be defined as the inerts e in the polymerization system, the component of promptly in polymerization system, not reacting.

Fluid one construed is in the material of their liquid state or supercritical state.

Dense thick fluid definition is the fluid medium that is in their liquid state or supercritical state, and it has above 300kg/m ³Density.

The polymerization in homogeneous phase system comprises that all its components disperse and mix on molecular level.In our discussion, the polymerization in homogeneous phase system is single dense thick phase, i.e. liquid phase or (overcritical) fluid phase.Should be noted that the polymerization system that we define does not comprise catalyst system, so catalyst system maybe or can not be dissolved in the polymerization system uniformly.Homogeneous system can have the concentration gradient zone, but should not be form unexpected in system, discontinuous variation on micron grade.When polymerization system is divided into more than a phase, it is uneven, but the more suitable nonhomogeneous system that is referred to as.

That below abridges is defined as: Me is a methyl, and Ph is a phenyl, and Et is an ethyl, and Pr is a propyl group; IPr is a sec.-propyl, and n-Pr is a n-propyl, and Bu is a butyl, and iBu is an isobutyl-; TBu is the tertiary butyl, and p-tBu is to the tertiary butyl, and TMS is a trimethyl silyl, and TIBA is a triisobutyl aluminium; MAO is a MAO, and pMe is to methyl, and flu is a fluorenyl, and cp is a cyclopentadienyl moiety.

Successive is represented the system of continual or the running that do not stop.For example, the successive process for preparing polymkeric substance is the reactant successive is incorporated in one or more reactor drums and the polymeric articles successive withdraws from process.

Slurry polymerization refers to the polymerization method that wherein in comprising the polymerisation medium of at least one extra phase, forms the solid polymer phase.Extra steam, liquid, (overcritical) fluid, liquid/liquid or the fluid/liquid phase of can comprising mutually in the polymerisation medium.If polymerisation medium is made up of vapor phase and liquid phase, then polymkeric substance rests in the liquid phase.

Solution polymerization refers to the wherein polymerization method of polymer dissolution in liquid or (overcritical) polymerizable fluid medium, and wherein polymerisation medium can comprise unreacted monomer, one or more inert solvents or their blend.Solution polymerization comprises the polymerization in homogeneous phase system.

Supercritical polymerization refers to the polymerization method that polymerisation medium wherein is in the supercutical fluid phase.

The mass polymerization polymerizable fluid system wherein of referring to comprises the inert solvent that is less than 40wt% or the polymerization method of thinner.Preferred mass polymerization comprises and is less than 30wt%, or is less than 20wt%, or is less than 10wt%, or is less than 5wt%, or is less than inert solvent or the thinner of 1wt%.Product polymer can be dissolved in the polymerisation medium or can be independent solid phase form, as slurry polymerization.In this term, the slurry polymerization medium that wherein in comprising the liquid that is less than 40wt% inert solvent or thinner or polymerizable fluid medium, forms solid polymer particle will refer to bulk slurry polymerization method or body heterogeneous polymerization method.Wherein polymerisate is dissolved in and comprises the liquid that is less than 40wt% inert solvent or thinner or the polymerization method of fluid phase-polymerization medium will refer to body polymerization in homogeneous phase method.Wherein polymerisate is dissolved in to comprise and is less than 40wt% and (preferably is less than 30wt%; Or be less than 20wt%; Or be less than 10wt%, and or being less than 5wt%, or being less than 1wt%) inert solvent or the liquid of thinner or the polymerization method in the fluid phase-polymerization medium will refer to the bulk solution polymerization method.Wherein polymerisate is dissolved in to comprise and is less than 40wt% and (preferably is less than 30wt%; Or be less than 20wt%; Or be less than 10wt%; Or be less than 5wt%, or being less than 1wt%) polymerization method in (overcritical) polymerizable fluid medium of inert solvent or thinner will refer to body homogeneous phase supercritical polymerization process.

The homogeneous phase supercritical polymerization should be distinguished with heterogeneous supercritical polymerization mutually, for example for instance, overcritical slurry process, wherein the latter carries out in mutually at supercutical fluid, but in polymerisation medium, forms second phase of being made up of solid polymer particle.Similarly, body homogeneous phase supercritical polymerization should with bulk solution synizesis difference, wherein the latter with (overcritical) polymerizable fluid medium different liquid in carry out.

The Tc of polymkeric substance and melt temperature are used TA Instruments 2920 dsc measurements with dsc (DSC).10mg molded polymer or plasticizing polymerization thing are sealed in the aluminium dish and at room temperature are loaded in the equipment.Fusion data (heating) first are higher than temperature of fusion at least and obtain for 30 ℃ through with the heating rate of 10 ℃/min sample being heated to, and are 220 ℃ for Vestolen PP 7052 typically.Under this temperature, sample is kept at least 5 minutes to destroy its thermal history.The crystallization data are cooled to be lower than Tc with sample from melt through the rate of cooling with 20 ℃/min and obtain at least 50 ℃, are-50 ℃ for Vestolen PP 7052 typically.Under this temperature, sample was kept 5 minutes at least, and heat to obtain extra fusion data (second-heating) with 10 ℃/min at last.Analyze beginning and peak temperature that heat absorption melting transition (first and second-heating) and heat release crystalline transition are used to change.Except as otherwise noted, then the melt temperature of report is the peak melt temperature from second-heating.For the polymkeric substance that shows multiplet, fusing point (or melt temperature) be defined as from the peak melt temperature of DSC fusion track (promptly with this TR in the thermal response of maximum caloric receptivity relevant); Similarly, Tc be defined as peak Tc from DSC crystallization track (promptly with this TR in exothermic maximum calorimetric response relevant).The DSC area under a curve is used to measure transition heat (melting heat during fusing, H _fOr the heat of crystallization during crystallization, H _c).

The present invention relates to a kind ofly be used for from the economic separation of the lower-molecular-weight component of the reaction medium of polymerization system and reclaim the method for polymkeric substance, be preferably the polymerization system that WO2004/026921 describes.The step that the polymerization method of describing among the WO2004/026921 comprises has: in polymerization system; Olefinic monomer with three or more a plurality of carbon atoms; With alkene and/or diolefine comonomer and one or more metallocene catalyst compound in the optional broad range, one or more acvators and optional inert diluent or solvent are contacting under the temperature of the solid-liquid transformation temperature that is higher than polymerization system with under being not less than the following 10MPa of polymerization system cloud point pressure and pressure less than 200MPa.From the elute of polymerization reactor, promptly polymerisation medium comprises unreacted monomer and optional comonomers, the thinner of any existence or solvent, and polymer product.In the present invention, the polymerisation medium that leaves aforementioned polymerization process directly in reliever, optional preheating.Reliever is positioned at the ingress of fluid-liquid phase separation container.Reliever is reduced to the pressure that is lower than cloud point pressure with the pressure of polymerisation medium fast and comprises the phase that is rich in polymkeric substance with formation and be rich in monomeric two-phase mixture mutually.The temperature of preferred polymeric medium is higher than the Tc of polymkeric substance in the polymerisation medium.Be rich in monomeric phase be rich in polymkeric substance in the fluid-liquid phase separation container through gravity settling separation, and isolating being rich in is recycled in the polymerization system after monomeric phase deals with slightly.

After being rich in monomer and the decompression mutually of being rich in polymkeric substance in the polymerisation medium; Preferably be reduced to pressure that is lower than below the cloud point pressure and the temperature that is higher than the polymer crystallization temperature (favourable for being higher than 10 ℃ of Tcs at least, perhaps be higher than at least 20 ℃ of Tcs, perhaps be higher than at least 50 ℃ of Tcs; If perhaps polymkeric substance does not have Tc then is higher than 80 ℃; Preferably be higher than 90 ℃, preferably be higher than 100 ℃), typically have visibly different density.Typically differing 0.2g/mL or more between two kinds of density, optionally is 0.3g/mL or more, perhaps 0.4g/mL or more, perhaps 0.5g/mL or more, perhaps 0.6 unit or more.In a useful embodiment, be retained in the solution polymkeric substance or molten state, after it leaves phase separation container.In preferred embodiments, the pressure high 7 to 100MPa of the pressure ratio separation vessel (for example HP separator) of (if used more than one reactor drum then at least one reactor drum) in the reactor drum, preferred high 15 to 75MPa and 25 to 50MPa.

In an embodiment of method, do not comprise that preferably the polymerization system of inert solvent prepares the polymkeric substance that is rich in propylene under the pressure of temperature that is higher than the polymerisation medium Tc and the cloud point pressure that is higher than polymerisation medium.This single-phase polymerisation medium does not further heat directly to possibly being in the reliever of pressure loading valve.Reliever fast; Typically the pressure of polymerisation medium is reduced to the pressure (also typically being lower than the pressure of spinodal boundary) that is lower than polymerisation medium cloud point pressure, comprises the phase that is rich in polymkeric substance with formation and be rich in monomeric two-phase mixture mutually with 2MPa/sec or higher speed (being preferably 6MPa/sec or higher).Direct result as fast decompression; Be rich in monomeric phase be rich in polymkeric substance in the fluid-liquid phase-separating device, be easy to separate through gravity settling; And isolating being rich in is recycled in the polymerization system after monomeric phase deals with slightly, saidly deals with the cooling that can comprise logistics slightly, from logistics, removes some hydrogen; Remove any sedimentary low-molecular weight polymer, and/or dry logistics in drying bed.What be rich in polymkeric substance directly removes any residual unreacted monomer or other volatile constituents mutually in the devolatilisation system.

Special; For polymerization method is the embodiment of body homogeneous phase supercritical polymerization process (the for example polymerization method of WO2004/026921); Method disclosed herein provides a kind of valid approach to be used for that lower-molecular-weight component with polymerisation medium separates with polymkeric substance and this lower-molecular-weight component has been recycled to and has been rich in monomeric recirculation stream; And wherein polymer product has propylene and the optional comonomers as its principal monomer, and the instance of this situation is overcritical Vestolen PP 7052 polymerization (SCPP).With discussed in detail, realize that for example, Vestolen PP 7052-propylene gathers (propylene-ethylene)-mixtures such as propylene-ethylene effective the separation through favourable utilization cloud point and the solid-liquid facies relationship relevant with alkene or alkene mixture of monomer and polymkeric substance as following.

In preferred embodiments; The present invention relates to be used for polymerisation medium with any polymerization system of describing derived from the WO2004/026921 invention is separated into and is rich in monomeric phase and is rich in polymkeric substance mutually; And in follow-up process of removing odor component, reclaim polymkeric substance; Be rich in mutually monomericly with reclaiming of economy, turn back in the polymerization process after dealing with slightly, therefore to obtain the method that minimum actual investment and running expense are used for the commerce execution of aforementioned polymerization method with efficient manner.Polymerisation medium derived from this polymerization method is in the supercutical fluid state, and can by single supercutical fluid mutually or two-phase fluid-fluid or fluid-liquid mixture form.The lower-molecular-weight component of polymerisation medium can only comprise the unreacted monomer of polymerization; Perhaps choose wantonly and can comprise inert solvent with the concentration that equals 40wt%, the polymeric constituent of polymerisation medium can comprise the blend (for example those disclosed among the WO2004/20691) of separate polymer or two or more polymkeric substance.This method preferably is made up of the steps of order below a series of: (a) through reliever the pressure of polymerisation medium is reduced to the pressure that is lower than cloud point pressure; But this pressure is enough high to avoid being rich in monomeric mutually all or part of evaporation, causes forming two-phase mixture-low-density and is rich in monomeric phase and is rich in polymkeric substance mutually with highdensity; Two-phase fluid-fluid or the fluid-liquid mixture that (b) will leave reliever are transferred to and are designed with sufficient size to provide enough residence time (typically more than 1 minute; Preferably between 1 and 30 minute) the gravity settling device in; More preferably between 1 to 15 minute, sedimentation is upper strata (being rich in monomeric phase) and lower floor (being rich in polymkeric substance mutually) so that be separated also with two; (c) phase transition that will be rich in polymkeric substance constantly reduce pressure in the placed in-line flash chamber in case from be rich in polymkeric substance mutually progressively remove residual monomer and solvent.These containers can heat insulationly turn round, and perhaps in them can use heating medium heated polymerizable thing solution to reduce the residue volatilization content of polymkeric substance; (d) will be rich in monomeric directly being recycled in the polymerization charge system mutually need not further handle.This a series of step comprises all schemes of WO2004/02691 polymerization method, and only comprises that requirement reclaims the step that monomeric minimum number mutually is rich in polymkeric substance and recycling.These steps can be through 1) increase optional step, 2) operational condition is limited in the optimum range, and 3) limit the composition improvement of polymerisation medium itself.During these improve each is discussed as follows:

Increase optional process step

Can comprise and the heating steps (referring to the lower section) that is rich in monomeric heat exchange mutually (be heat integration-referring to following); This step makes the temperature of polymerisation medium be elevated to enough height and is separated with the upper reaches or the inner solid-liquid that takes place that stops fluid-liquid phase separation container (also being called HP separator or HPS); To such an extent as to it is and enough high when passing reliever (pressure loading valve) reduction pressure; There is such pressure, wherein under sufficiently high pressure, takes place effectively polymerisation medium is separated into and be rich in monomeric phase and the pressure mutually that is rich in polymkeric substance to prevent to be rich in monomeric mutually all or part of evaporation.

The step of catalyst deactivation below is discussed.This will comprise the optional dry siccative that is rich in the recirculation stream of monomeric phase that uses.

As following discussion, the step of removing dealkylation promptly can include but not limited to single or multiple flash chamber, separation column or hydrogenation bed.Be used for can being applied to the whole monomeric recirculation stream that is rich in except that the processing of dealkylation, perhaps hydrogen removes under the situation that requires to allow therein, is applied to be rich in the only part of monomeric recirculation stream, or slip-stream.

With being rich in the temperature that the monomeric temperature that is cooled to wherein to be rich in monomeric phase has mutually surpassed the temperature of polymerization system charging.This can with pound out jar (knockout pot) or filter coupling when removing cooling from be rich in monomeric mutually sedimentary polymkeric substance.Referring to following this part more detailed part.

Limit operational condition

Be separated TemperatureCan change, particularly use the system that heats, so the restriction of temperature will combine with the heating steps of above increase for wherein optional.The Policy description that when using well heater, dwindles TR is following.

Be separated PressureCan be based on and limit the principle of optimum range between the highest possible pressure (cloud point) point pressure and the minimum possible pressure (wherein being rich in the pressure of monomeric mutually all or part of evaporation) and change.First change will use the spinodal terminal pressure to replace cloud point pressure, and follow-up then change can progressively be lower than spinodal border, minimum value and progressively is higher than vapor pressure (being rich in monomeric mutually all or part of evaporation) this scope is narrowed down through setting peak.These notions are in following explanation.The benefit of optimization pressure is to minimize product and reclaims and the total cost that is rich in monomeric recirculation system mutually.Higher pressure has improved the cost (flashing off more monomer) that product reclaims, but has reduced cost-less pumping, the refrigerative cost that is rich in monomeric phase recycling.

Use spinodal to decompose to be used for wild phase to separate to be included in separating pressure (as above description) and pass through reliever Reduce the speed of pressureBoth last setting changings, generalized as following institute.The benefit that spinodal decomposes is the cost of investment that reliever downstream two break away from and therefore saved the HPS container faster mutually.

Be rich in monomeric phase be rich in polymkeric substance Difference on the densityIn with the lower section, discuss, it relates to separating pressure.The scope of phase density difference can be selected with the cost of investment that helps to handle and save the HPS container faster that requires.

Limit the composition of polymerisation medium

Polymerisation medium can change on inert solvent content.But, preferably do not have solvent, promptly wherein in the solution of polymkeric substance in unreacted monomeric mixture.

Polymerisation medium can further change on polymeric type, and the polymkeric substance of its desired is the polymkeric substance that is rich in propylene, and wherein propylene is principal monomer (promptly surpassing 50mol%).Low density (the 0.915g/cm that can not in body liquid slurry method, prepare in preferred embodiments, ³Or lower) polymkeric substance can here prepare.

Polymerisation medium can further change on the thermodynamic state of single-phase supercutical fluid.Uniting of these three kinds of changes gives you the particularly preferred embodiment relevant with SCPP, wherein can on phase separation temperature and pressure, unite to provide point-device control with these changes.

Catalyst system

If under the disclosed polymerizing condition of catalyst system enough activity are arranged here, method then described herein can use any can polymerization monomeric catalyzer disclosed herein (also being called catalyst system (being catalyst compound (also referring to catalyst precursor) and acvator and optional activator promotor and/or scavenging agent)).Therefore the 3-10 group 4 transition metal can form suitable polymerizing catalyst.Suitable olefin polymerization catalysis compound can with ethylenic unsaturation polymerization of olefin using catalyst or in addition coupling.Illustrative rather than restrictive olefin polymerization catalysis compound comprises Ziegler Natta catalyst compound, metallocene catalyst compound and other non-metallocene catalyst compound.Illustrative rather than restrictive acvator comprises aikyiaiurnirsoxan beta, for example MAO and ionize acvator, for example non-coordinate negatively charged ion.Useful non-coordination anion comprises trimethyl ammonium four (pentafluorophenyl group) borate, N, accelerine four (pentafluorophenyl group) borate, triphenylcarbenium four (perfluorophenyl) borate and N, accelerine four (perfluorophenyl) borate.Obtainable useful aikyiaiurnirsoxan beta from commercial resource, Akzo-Nobel Corporation for example, and comprise MAO, MMAO-3A, MMAO-12 and PMAO-IP.The coupling of the coupling of the coupling of aikyiaiurnirsoxan beta, non-coordination anion acvator and aikyiaiurnirsoxan beta and non-coordination anion acvator can be used for practice of the present invention.

When utilizing the supercritical polymerization condition, polymerization in homogeneous phase catalyzer for example metallocenyl catalyzer and other unit point homogeneous catalysis immunomodulator compounds possibly be favourable.For example, when polypropylene under super critical condition, useful especially metalloscene catalyst and non-metallocene catalyst compound are to incorporate U.S.Serial No.10/667 of the present invention into through reference, 585 with US 2006-0293474 in those disclosed.

Useful preferred catalyzer and activator compound and their coupling have been listed here for 21 to 85 pages of WO 2004/026921.The 29th page of [0101] section to the 66th page the 4th ranks of WO 2004/026921 have gone out useful preferred especially catalyst compound here.Here useful preferred activator compound comprises those that [00135] section of the 77-78 page or leaf of WO 2004/026921 is listed.11/714 of submission on March 6th, 2007; 546 (for example disclose useful another group catalyst compound and acvator here; The catalyst system that comprises one or more acvators and one or more non-metallocene metal centers; The heteroaryl ligand catalyst compound, wherein metal is selected from the 4th, 5,6 families of the periodic table of elements, group of the lanthanides or actinium series).WO 03/040095, and WO 03/040201, and WO 03/040202, and WO 03/040233, among WO 03/040442 and the US 7,087,690 more detailed description this catalyst compound.

Here other useful catalyst compound and system comprise following document those disclosed: US 6,897,276, and US 7; 091,292, WO 2006/066126, through being used at the unconventional catalyzer of solution isotactic propylene polymerization of use high flux screening technological development; Boussie, people such as Thomas R., Angewandte Chemie; InternationalEdition (2006), 45 (20), 3278-3283.

Useful especially catalyzer comprises: racemize-dimetylsilyl-two (5,6,7,8-tetrahydroxy-5,5,8,8-tetramethyl--2-methyl isophthalic acid H-benzindene) dimethyl-hafnium; Dimetylsilyl (tetramethyl-ring pentadienyl) (dodecyl is amino) dimethyl-titanium; 1; 1 '-two (4-triethylsilyl phenyl) methylene radical-(cyclopentadienyl moiety) (2,7-two-tertiary butyl-9-fluorenyl) dimethyl-hafnium, dimetylsilyl two (indenyl) dimethyl-hafnium; Dimetylsilyl two (tetrahydroxy indenyl) zirconium dichloride; Dimetylsilyl two (2-methyl indenyl) zirconium dichloride, dimetylsilyl two (2-methylfluorenyl) zirconium dichloride, dimetylsilyl two (2-methyl-5; 7-propyl group indenyl) zirconium dichloride; Dimetylsilyl two (2-methyl-5-phenyl indenyl) zirconium dichloride, dimetylsilyl two (2-ethyl-5-phenyl indenyl) zirconium dichloride, dimetylsilyl two (2-methyl-4-phenyl indenyl) zirconium dichloride and phenylbenzene methylene radical (cyclopentadienyl moiety) (fluorenyl) dimethyl-hafnium.Useful catalysts also comprises dialkyl group (for example dimethyl-) analogue of any dihalide catalyzer of above name.

Useful especially Metallocenic compound comprises Me ₂Si-two (2-R, 4-Phl-indenyl) MX ₂, wherein R is alkyl group (a for example methyl), and Phl is phenyl or substituted phenyl, and M is Hf, and Zr or Ti, X are halogen or alkyl group (for example Cl or methyl).Useful especially Metallocenic compound comprises: dimetylsilyl-two (2-methyl, 4-phenyl-indenyl) dimethyl-(or dichloride) zirconium, dimetylsilyl-two (2-methyl; 4-(3 '; 5 '-two-trimethylphenylmethane base)-and indenyl) dimethyl-(or dichloride) zirconium, dimetylsilyl-two (2-methyl, 4-naphthalene indenyl) dimethyl-(or dichloride) zirconium and dimetylsilyl-two (2-methyl; 4-(3 ', 5 '-the di-t-butyl naphthyl)-indenyl) dimethyl-(or dichloride) zirconium.

In preferred embodiments; Catalyst system used herein comprises acvator (preferred non-coordination anion; Trimethyl ammonium four (pentafluorophenyl group) borate for example, N, accelerine four (pentafluorophenyl group) borate; Triphenylcarbenium four (perfluorophenyl) borate or N, accelerine four (perfluorophenyl) borate) and the catalyst compound of representing through following formula:

M wherein ¹Be selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten (preferred zirconium and/or hafnium); R ¹And R ²Identical or different, and be selected from Wasserstoffatoms, C ₁-C ₁₀Alkyl, C ₁-C ₁₀Alkoxyl group, C ₆-C ₁₀Aryl, C ₆-C ₁₀Aryloxy, C ₂-C ₁₀Thiazolinyl, C ₂-C ₄₀Thiazolinyl, C ₇-C ₄₀Aralkyl, C ₇-C ₄₀Alkaryl, C ₈-C ₄₀Arylalkenyl, OH group or halogen atom; Or the optional alkyl of using, (the preferred R of one or more the substituted conjugated dienes in three (alkyl) silyls or alkyl three (alkyl) the silyl alkyl ¹And R ²Be alkyl, for example methyl or ethyl, or halogen root, for example chlorine root); R ³-R ¹²Identical or different, and be selected from Wasserstoffatoms, halogen atom, C ₁-C ₁₀Halogenated or not halogenated alkyl, C ₆-C ₁₀Halogenated or not halogenated aryl, C ₂-C ₁₀Halogenated or not halogenated thiazolinyl, C ₇-C ₄₀Halogenated or not halogenated aralkyl, C ₇-C ₄₀Halogenated or not halogenated alkaryl, C ₈-C ₄₀Halogenated or not halogenated arylalkenyl ,-NR ' ₂,-SR ' ,-OR ' ,-OSiR ' ₃Or-PR ' ₂Group, wherein R ' is a halogen atom, C ₁-C ₁₀Alkyl or C ₆-C ₁₀One of aryl; Perhaps R ⁵To R ⁷In the group of two or more vicinities can form one or more rings (preferred R with the atom that connects them ³Be methyl, ethyl or butyl), and adjacent R ¹¹And R ¹²Can form one or more saturated rings or aromatic ring (preferred R ¹¹And R ¹²Merge to form substituted or unsubstituted naphthyl with phenyl ring); R ¹³Be selected from:

-B (R ¹⁴)-,-Al (R ¹⁴)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO ₂-,-N (R ¹⁴)-,-CO-,-P (R ¹⁴)-,-P (O) (R ¹⁴)-,-B (NR ¹⁴R ¹⁵)-with-B [N (SiR ¹⁴R ¹⁵R ¹⁶) ₂]-, R ¹⁴, R ¹⁵And R ¹⁶Separate hydrogen, halogen, the C of being selected from ₁-C ₂₀Alkyl, C ₆-C ₃₀Aryl, C ₁-C ₂₀Alkoxyl group, C ₂-C ₂₀Thiazolinyl, C ₇-C ₄₀Aralkyl, C ₈-C ₄₀Arylalkenyl and C ₇-C ₄₀Alkaryl, perhaps R ¹⁴And R ¹⁵Atom with connecting them forms ring; And M ³Be selected from carbon, silicon, germanium and tin, perhaps R ¹³Represent with following formula:

R wherein ¹⁷To R ²⁴With R ¹And R ²Definition identical, perhaps R ¹⁷To R ²⁴In two or more adjacent groups, comprise R ²⁰And R ²¹, form one or more rings, M with the atom that connects them ²Be carbon, silicon, germanium or tin (preferred R ¹³Be dimetylsilyl or diphenylmethyl siloyl group).

The mol ratio of the catalyzer/acvator that uses in 000 to 100: 1 the scope, more preferably 1: 5000 to 10: 1, most preferably is 1: 100 to 1: 1 preferably at 1: 10.In one embodiment, promotor can be used for each alkyl on have 1 to 10 carbon atom three (alkyl) aluminum compound associating.Can also use the mixture of active cocatalyst.Because the ability of their favourable removals of contamination also possibly used these aluminum compounds removal of contamination from polyblend, for example oxygen, water and aldehyde.Preferred aluminum compound comprises the trialkyl aluminium compound that has 1 to 6 carbon atom on each alkyl, and those alkyl are methyl when special, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, the compound of neo-pentyl and isopentyl.The mol ratio of metal complex and aluminum compound is preferably 1: 10,000 to 100: 1, more preferably 1: 1000 to 10: 1, most preferably is 1: 500 to 1: 1.Most preferred borine active cocatalyst comprises strong lewis acid, particularly three (pentafluorophenyl group) borine.In another embodiment, for example zinc ethyl and triethyl aluminum coupling of two kinds of catalyst compound and at least a acvator and activator promotor.

Catalyst system used herein or their any component can typically be loaded on the organic or inorganic carrier by load.Suitable carriers comprises silicon oxide, aluminum oxide, and clay, zeolite, magnesium chloride, polyoxyethylene glycol, according to vinylbenzene, polyester, polymeric amide, polypeptide and analogue.The polymerizability carrier can be crosslinked or uncrosslinked.Preferred carrier comprises silicon-dioxide and incinerating silicon-dioxide.

Method described herein typically is used to prepare C3 or the more polymkeric substance of higher alkene, for example acrylic polymer.Preferred polymkeric substance comprises that the Vestolen PP 7052 with 0 to 50mol% comonomer (is preferably 0.5 to 25mol%; Be preferably 1 to 15mol%; Be preferably 2 to 10mol%), wherein comonomer is selected from ethene and linear, branching or ring-type C4 to the alkene of C30, is preferably alhpa olefin.Preferred comonomer comprises ethene, butylene, hexene, octene, norbornylene, 3,5,5 ,-trimethylammonium-1-hexene, vinylbenzene, p-methylstyrene, 4-methyl-1-pentene, Dicyclopentadiene (DCPD) and analogue.Diolefine can also be as independent comonomer or as the 3rd-or the 4th-monomer.Useful diolefine comprises norbornadiene, hexadiene, and divinyl, octadiene or any other C4 are to linear, branching or the cyclic diolefine of C30.

Monomer, comonomer, the polymerisation medium of solvent and thinner comprises the propylene monomer of 55-100wt%, 0 to 45wt% copolymerized monomer mixture; This copolymerized monomer mixture comprises at least a ethene that is selected from, butylene, hexene, octene; Decene, 4-methyl-1-pentene, Dicyclopentadiene (DCPD), norbornylene; The terminal olefin of C4-C2000, the α of C4-C2000, the α of interior-diolefine and C4-C2000; The comonomer of ω-diolefine, condition are if comonomer is an ethene, and it is with the amount existence of 0 to 20wt% (based on the monomer that gets into reactor drum and the weight of comonomer).Optionally; C3 or more senior monomer (preferred propylene) are with 40 weight % or more amount (based on the weight of monomer that gets into reactor drum and comonomer [being 40wt% or more based on the weight of polymerization system optionally perhaps]) existence; And it [perhaps optionally is 0 to 50wt% that there be (preferred 1 to 45mol%) (based on the monomer and the comonomer material that merge, condition is if comonomer is an ethene, and its amount with 0.5 to 20mol% exists) in comonomer with 0 to 50mol% comonomer; Weight based on polymerization system; Condition is if comonomer is an ethene, and its amount with 0.5 to 20wt% exists], be 1 to 50wt% optionally perhaps based on the monomer of entering reactor drum and the weight of comonomer; Condition is that its amount with 0.5 to 20wt% exists if comonomer is an ethene.

Method of the present invention can be used one or more catalyzer in placed in-line or parallelly connected many reactor drums.Many catalyzer can use in any reactor drum of polymerization reactor part of the present invention.Because practice preferably is no more than five kinds of catalyzer in any given reactor drum, and more preferably no more than three kinds of catalyzer.In the different reactor drums separately of reactor drum of the present invention part, method of the present invention can be used identical or different catalyst or catalyst mixture.Because practice, the preferred use is no more than ten kinds of catalyzer and more preferably no more than six kinds of catalyzer in polymerization method of the present invention.

The catalyzer that uses in the method for the invention can be dissolved in the polymerisation medium uniformly or in reactor drum, can form heterogeneous solid phase.The preferred catalyzer of uniform dissolution that uses is operated.When catalyzer was present in the polymerization reactor with solid phase, it can be load or unsupported.Method of the present invention can be used any homogeneous and the associating of heterogeneous catalyzer in the one or more independent reactor drum that is present in polymerization reactor zone simultaneously, and any reactor drum in polyreaction promptly of the present invention zone can comprise one or more homogeneous catalysts and one or more heterogeneous catalyst simultaneously.

Method of the present invention can be used any homogeneous that is used for polymerization reactor of the present invention part and the associating of heterogeneous catalyst.These unite situation and the situation when some or all of reactor drums use more than a kind of catalyzer of using independent catalyzer when some or all of reactor drums that comprise.One or more catalyzer that use in the method for the present invention can load on the particle, and it can be dispersed in the polymerizable fluid medium or can be included in the fixed beds.

When the granules of catalyst of load was dispersed in the polymerisation medium, they can be stayed in the polymerisate or can before it reclaims from reactor effluent, from product, separate in the fluid-liquid separating step in the polymerization reactor portion downstream.If granules of catalyst reclaims, can they be abandoned maybe can the regenerate back or the back recycling of not regenerating.Catalyzer can also load on the carrier of structure, for example comprises monolithic building stones straight or tortuous passageway, reactor wall, internal pipeline etc.

When catalyzer is load, preferably use dispersed particles to operate.When catalyst cupport is on dispersed particles, preferably there is not the operation of catalyst recovery, be about to catalyzer and stay in the polymerisate of method of the present invention.The catalyst dissolution of most preferably inciting somebody to action not load is in fluid reaction medium.Catalyzer can be incorporated in the reactor drum with many kinds of methods.For example, catalyzer can be with containing monomeric material or introducing separately.

In addition, catalyzer can be introduced in the reactor drum through one or more import and export.If a plurality of import and export are used to introduce catalyzer, these import and export can be placed on the identical or different position of essence on the length direction of reactor drum.If a plurality of import and export are used to introduce catalyzer, the component through independent import and export charging and the amount of catalyzer can be identical or different.Amount through different import and export adjustment catalyzer and type can modulation polymer character, for example MWD, composition, composition distribution, crystallinity etc.

Useful reactor drum comprise tubular type, loop and or autoclave, when using more than a reactor drum, it can be with any series arrangement.In preferred embodiments, two or more reactor drums (can be the reactor drum of identical or different kind) are arranged in parallel and the elute of each reactor drum is incorporated in the identical phase separation container.Preferred all reactor drums under high pressure turn round preferably in single-phase (for example supercritical phase).In preferred embodiments; There are two reactor drums in supercritical phase (preferred two reactor drums all are tubular reactors), to turn round and the elute logistics merged before or after decompression and the logistics that merges is incorporated in the phase separation container; This container can have or not have stirring tool, for example mixing tank.

Polymerization method described herein runs well in tubular reactor and autoclave (also being called agitator tank reactor).Autoclave can with intermittently or the successive mode turn round.For better yield-power is provided, and therefore be lowered into the product cost, preferably successive running in commercial operation.Preferred tubular reactor turns round in a continuous manner.Typically, autoclave has 1: 1 to 20: 1 slenderness ratio (being preferably 4: 1 to 20: 1) and (equaling 2000RPM) a plurality of blade whisking appliances at a high speed typically is installed.When autoclave has low slenderness ratio (for example less than four), feed stream typically is expelled in only position of reactor length.Have large diameter reactor drum and can near the same position on the reactor length, have a plurality of outlets that are injected into, but their radial distributions allow parallel feeding component faster and reactor component.In the situation of agitator tank reactor, introducing catalyzer that maybe be independent and normally preferred.This introducing has stoped the possibility that forms focus in the intake zone that between the stirring area of mixing point and reactor drum, does not stir.Also be possible and be preferred sometimes on the reactor length direction, on two or more positions, injecting.For example, slenderness ratio is in about 4: 1 to 20: 1 the reactor drum therein, and reactor drum preferably comprises and equals six different injection phases.In addition, in bigger autoclave, the device of one or more crosswise fixed is supporting high speed agitator.These stationary devices can also be divided into two or more zones with autoclave.Mixing blade on the whisking appliance can be different in each zone, and this allows a large amount of independently in various degree piston flow and back-mixings in distinct area.Two or more autoclaves with one or more zones can be connected in series to increase the residence time or modulation polymer structure by successive.As above-mentioned, the successive reactors in series typically has the reactor drum of two or more continuous connections, and wherein the elute of at least one upstream reactor is fed to the next reactor drum in placed in-line downstream.Except the elute of upstream reactor, the charging of any continuous tandem reactor can use the associating of any extra monomer, catalyzer or fresh solvent or recycling feed stream to strengthen.Two or more reactor drums can also be with the structural arrangement of parallel connection.This independent arm that is arranged in parallel refers to the reactor drum string.These reactor drum strings originally are that the reactor drum that can comprise the associating of a reactor drum or formation series connection and parallel reactor is successively connected continuously.

Tubular reactor can also be used for method disclosed herein, and more particularly tubular reactor can equal running under about 350MPa.Tubular reactor is equipped with external cooler and one or more decanting point along (tubular type) reaction zone.As in the autoclave, these decanting points are as the inlet point of the mixture of monomer (for example propylene), one or more comonomers, catalyzer or these materials.In tubular reactor, with respect to autoclave, external cooler allows to increase monomeric conversion usually, and wherein low surface has hindered any significant heat extraction to the ratio of volume.Tubular reactor has the special output valve that can transmit pressure surge along pipe backward.This shockwave helps to remove any polymer residue that on reactor wall between on-stream period, forms.Optionally, tubular reactor can be made into level and smooth, unpolished internal surface to solve the wall deposition.Tubular reactor can have the length of 100-2000 rice or 100-4000 rice, and can have the internal diameter (optionally less than 10cm) less than 12.5cm equaling running under the pressure of 360MPa usually.Typically, tubular reactor has 10: 1 to 50,000: 1 slenderness ratio and can alongst comprise and equal 10 different injection phases.

Reactor drum string with paired autoclave of tubular reactor also can be used for method of the present invention.In this instance, autoclave typically before the tubular reactor or two types reactor drum form the independent string of parallel reactor configuration.This system can be in autoclave and particularly on many points of the length direction of pipe, is injected additional catalysts and/or feed component.

In autoclave and tubular reactor, during injection, material preferably is cooled near envrionment temperature or following with the maximum cooling value that provides and therefore in the scope of maximum operating temp restriction, obtain aggregate maximum produce amount.In the autoclave operation, if first mixing zone has some air-teturning mixed characteristics, running preheater during startup, but this was just dispensable after reaction reached plateau.In tubular reactor, double fastener telescopic first part is heated rather than cools off and carry out successive operation.Useful tubular reactor is characterised in that piston flow.Piston flow means that flow pattern has smallest radial flow rate difference.In autoclave and tubular reactor, catalyzer not only can inject in the ingress, and chooses wantonly along injecting on one or more points of reactor drum.It can be identical or different that catalyst feed is injected according to content, density, concentration etc. with other decanting points at inlet.Select the different catalyst material to allow the polymer design customization.At reactor drum delivery valve place, pressure is reduced to and is lower than the isolating level of critical phase that produces.Therefore, the downstream separation container can comprise the phase that is rich in polymkeric substance and contain polymkeric substance mutually with poor.Typically, the condition in this container remains on overcritical, and temperature remains on more than the polymeric articles Tc.The elute of autoclave or tubular reactor is decompression when getting into HP separator (HPS).

In any multiple reactor system described herein, only there is a reactor drum or to be higher than the operation down of solid-fluid phase transistion pressure and temperature (preferably being higher than fluid-fluid transistion pressure and temperature mutually), operates but all reactor drums can or be higher than under solid-flow graph phase transistion pressure and the temperature (preferably being higher than fluid-fluid transistion pressure and temperature mutually) in supercritical state in supercritical state.

Solvents/diluents

One embodiment of the invention are for separating in the mass polymerization medium that never comprises inert solvent or thinner and the recovery polymkeric substance.In this embodiment preferred, polymerisation medium is made up of the polymkeric substance and the residual catalyst component that are dissolved in the unreacted monomer.Preferably do not use solvent or thinner.

In another embodiment, solvents/diluents is used for polymerization system to prepare commercial useful product, makes the catalyst component dissolving, reduces the viscosity of polymerisation medium, perhaps is used for other purposes.In using the embodiment of solvents/diluents, the solvents/diluents that needs to use minimum with the commercial useful product of the preparation that obtains expectation, make the effects such as viscosity that catalyst component is stable, reduce polymerisation medium.In preferred embodiments, need in polymerisation medium, the concentration of solvent be 0.1 to 40wt%, perhaps 0.2 arrive 20wt%, perhaps 0.3 arrive 10wt%, perhaps 0.4 arrive 5wt%, perhaps 0.5 to 1wt% to obtain these effects.

The useful thinner of the present invention comprises one or more C ₂-C ₂₄Alkane, ethane for example, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane mixes hexane, isohexane, pentamethylene, hexanaphthene etc., monocyclic aromatic compound, for example toluene and YLENE.In some embodiments, thinner comprises the mixture of these thinners.In some embodiments, but preferably recycling of thinner.

In some embodiments, thinner comprises C ₄To C ₁₅₀Isoalkane, preferred C ₄To C ₁₀₀Isoalkane, preferred C ₄To C ₂₅Isoalkane, more preferably C ₄To C ₂₀Isoalkane.The density (ASTM 4052,15.6/15.6 ℃) of preferred these isoalkane is 0.67 to 0.83g/cm ³Scope in; Pour point is-40 ℃ or lower, is preferably-50 ℃ or lower, and 25 ℃ of following viscosity (445,25 ℃ of ASTM) are 0.5 to 20cSt; Molecular-weight average arrives in the scope of 300g/mol 100.Some suitable isoalkane are commercially available acquisition, and its trade name is ISOPAR (ExxonMobil Chemical Company, Houston TX), and at for example US6; 197,285,3,818; Describe to some extent in 105 and 3,439,088, and a series of isoalkane of selling with ISOPAR.Other suitable isoalkane also are purchased acquisition, and trade name is SHELLSOL (available from Shell), SOLTROL (available from Chevron Phillips) and SASOL (available from Sasol Limited).SHELLSOL is the product of Royal Dutch/Shell Group ofCompanies, for example Shellsol TM (boiling point=215-260 ℃).SOLTROL is the product of Chevron Phillips Chemical Co.LP, for example SOLTROL 220 (boiling point=233-280 ℃).SASOL is the product in Sasol Limited (Johannesburg, South Africa), for example SASOL LPA-210, SASOL-47 (boiling point=238-274 ℃).

In another embodiment, thinner comprises C ₄To C ₂₅NPH, preferred C ₄To C ₂₀NPH, C ₄To C ₁₅NPH, it preferably has the 0.1wt% of being less than, preferably has the 0.01wt% of a being less than aromatics.Some suitable NPHs are commercially available acquisitions, and its trade name is that (ExxonMobil Chemical Company HoustonTX), and is a series of NPHs of selling with NORPAR to NORPAR.In another embodiment, preferable absorbent comprises the aliphatic hydrocarbon that takes off aromatize that comprises NPH, isoalkane and naphthenic hydrocarbon mixture.Typically, they are C ₄To C ₂₅The mixture of NPH, isoalkane and naphthenic hydrocarbon, be preferably C ₅To C ₁₈, be preferably C ₅To C ₁₂They comprise very low-level aromatic hydrocarbons, preferably are less than 0.1, preferably are less than 0.01 aromatics.The suitable aliphatic hydrocarbon that takes off aromatize is commercially available acquisition, and its trade name is EXXSOL (ExxonMobilChemical Company, Houston TX), and is to take off aromatized fat family hydrocarbon with the series that EXXSOL sells.

11 to the 13 pages of Additional Informations that can find useful thinner at WO 2004/026921.

HP separator, recirculation system and downstream processing

In one embodiment of the invention; Polymerization as described in the WO2004/026921 (for example; Pressure is higher than the cloud point pressure of polymerisation medium) and polymerisation medium successive transfer (preferably not heating) in reliever (it can be a pressure loading valve), wherein pressure is reduced to (and preferred temperature is kept above the Tc of polymkeric substance in the polymerisation medium) below the cloud point pressure.This is favourable cause forming denseer thick; Be rich in the phase of polymkeric substance with not too dense thick be rich in mutually monomeric; Then it is transferred to the fluid-liquid separation vessel (also referring to phase separation container) that is called HP separator (HPS), wherein being rich in monomeric phase is two-layer through gravity settling separation typically with what be rich in polymkeric substance mutually.In preferred embodiments, the pressure (for example HP separator) high 7 to 100MPa, preferred 15 to 75MPa in the pressure ratio separation vessel in the reactor drum (if perhaps use more than a reactor drum then be at least one reactor drum), preferred 25 arrive 50MPa.

In another embodiment; Can change (crystallization) mutually to prevent the solid-liquid that HPS is rich in the phase of polymkeric substance through the temperature that heating is arranged in the device rising polymerisation medium at reliever (pressure loading valve) upper reaches; It can and take place along with the increase of polymer concentration or medium cooling, perhaps allows HPS under high pressure to operate and therefore avoids being rich in monomeric mutually all or part of evaporation.Typically being rich in monomeric top from HPS then is recycled to the reactor drum; And be rich in the one or more optional low pressure phase separators (LPS) that are arranged on the first phase separator downstream of typically being fed to mutually of polymkeric substance, and in the Zhongdao coupled devolatilization sundries-for example LIST moisture eliminator (DTB) or devolatilisation forcing machine.The working pressure of separator will reduce in the separator string usually; Cause in the downstream separator be rich in polymkeric substance mutually in polymkeric substance become denseer thick and consume and to compare light component with corresponding upper reaches phase concentration in the polymerization system, for example monomer and optional inert solvent/thinner.

Phase separation temperature

In embodiments of the invention, the optionally heating of the polymerisation medium at the optional reliever upper reaches minimizes in the polymerisation medium phasor is forced restricted portion.In order effectively to be separated, the enough height of temperature of the polymerisation medium of the ingress of reliever (pressure loading valve) in case the upper reaches of fluid-liquid phase separation vessel (HPS) or its inner solid-liquid that takes place be separated.To such an extent as to effectively phase separation temperature is also enough high when passing the reduction of reliever (pressure loading valve) pressure; Have such pressure, wherein polymerisation medium can take place effectively to be separated under sufficiently high pressure and be rich in monomeric phase and the pressure mutually that is rich in polymkeric substance to prevent to be rich in monomeric mutually all or part of evaporation.Satisfying the applicable operating restraint of temperature and pressure of these standards can be measured by the temperature-pressure phase diagram (type of for example describing among Fig. 2) of polymerisation medium.Because the heated polymerizable medium has increased cost of investment (installation of well heater); And increased running cost (consumption of hot effectiveness); If polymerization system is being operated above under the temperature of effective phase separation temperature standard, then the preferred embodiment of method is not used heating usually.Optionally; Wherein polymerisation medium is in the embodiment that is lower than the satisfied critical temperature that effectively is separated of requirement; To use heating to be higher than 0 to 100 ℃ of the desired minimum temperature of effectively being separated being elevated in the temperature of reliever (pressure loading valve) ingress, or 5 to 50 ℃, or 10 to 30 ℃.

Consider the standard of effective phase separation temperature, method of the present invention can be carried out under following temperature.In one embodiment; The temperature of polymerization system is higher than the solid-fluid phase transition temperature of the fluid reaction medium that under reactor pressure, contains polymkeric substance; Preferably than at least 5 ℃ of the solids of the fluid reaction medium that under reactor pressure, contains polymkeric substance-fluid phase transition temperature height, more preferably than these at least 10 ℃ of the fluid reaction medium solids that under reactor pressure, contains polymkeric substance-fluid phase transition point.In another embodiment, temperature is between 50 and 350 ℃, or between 60 and 250 ℃, or between 70 and 200 ℃, or between 80 and 180 ℃, or between 90 and 160 ℃, or between 100 and 140 ℃.

Spinodal decomposes

In the preferred embodiment of the invention; Reliever is designed to enough reduce pressure fast through the method that spinodal decomposes; And be reduced to optimum pressure; It causes the phase morphology (also being called common continuous morphology) of biphase interpenetrating(polymer)networks, the result of the expectation that it has be easy to be rich in polymkeric substance be rich in monomeric being separated and sedimentation fast in fluid-liquid gravity separation vessel (for example HPS).Spinodal decompose prevented to have the droplet that is rich in monomeric phase be dispersed in successive be rich in polymkeric substance mutually in very slow the separating and very slow sedimentation of being rich in monomeric phase and the phase that is rich in polymkeric substance of form; When the polymer concentration in the fluid surpasses threshold value; And it tends to the generation of nature when being arranged in the zone of phasor between fluid-liquid phase border (binode border) and the spinodal border when the temperature and pressure in the phase separation container, as among Fig. 2 through shown in the zone of drawing with cross-hatched.In the preferred embodiment of the invention, in the polymerisation medium concentration of polymkeric substance always be higher than above-mentioned threshold concentration (with conceptive as shown in Figure 1) and therefore these embodiments utilize the spinodal decomposition method to avoid the gravity settling problem.Embodiment (those that for example describe among the WO2004/026921) at the spinodal decomposition method that is used for the supercritical polymerization system; The pressure changing down that passes reliever (pressure loading valve) is 1MPa/sec or more; Perhaps 2MPa/sec or more; Perhaps 4MPa/sec or more, perhaps 6MPa/sec or more.

Pressure is separated

In all embodiments of the present invention; The pressure in reliever (pressure loading valve) downstream and fluid-liquid phase separation container (for example HPS) pressure inside are chosen as and are lower than cloud point pressure and with assurance fluid-liquid can take place and be separated; But this pressure is enough high, and it is being rich in more than the vapor pressure of monomeric phase to prevent to be rich in monomeric mutually all or part of evaporation.In preferred embodiments, be separated fast and sedimentation in order to impel, the pressure in the fluid-liquid phase separation container (for example HPS) is lower than the spinodal terminal pressure.In this preferred pressure scope, that is, be lower than spinodal pressure and be higher than the vapor pressure that is rich in monomeric phase, working pressure can be chosen as the pressure that can prove most economical.Higher pressure has reduced to carrying out recycling pumping or compression and has been rich in the cost of monomeric phase; But higher pressure has also reduced the speed that is separated and has caused the more highdensity monomeric phase that is rich in; The difference that it has reduced to be rich in the phase of polymkeric substance and has been rich in density between the monomeric phase; Settled speed in the fluid-liquid phase separation container that slowed down thus (for example HPS), and final requirement has bigger container.In one embodiment of the invention; The pressure in reliever (pressure loading valve) downstream and fluid-liquid phase separation container (HPS) pressure inside are lower than the pressure on spinodal border; Perhaps than the low 1MPa at least of spinodal terminal pressure; Perhaps than the low 5MPa at least of spinodal terminal pressure, perhaps than the low 10MPa at least of spinodal terminal pressure.In one embodiment, this pressure is not less than the evaporating pressure that is rich in monomeric phase, is not less than 0.2MPa than the evaporating pressure height that is rich in monomeric phase, is not less than 1MPa, perhaps is not less than 10MPa.In another embodiment, be rich in the phase of polymkeric substance and the density variation that is rich between the monomeric phase is 0.1g/mL at least, perhaps 0.2g/mL at least, perhaps 0.3g/mL at least, perhaps 0.4g/mL, perhaps 0.5g/mL or 0.6g/mL at least at least at least.The density of phase is measured through common volume method under the pressure and temperature of any regulation, for example passes through the weight of the phase of measurement known volume.In another embodiment, the pressure in the phase separation container (for example HPS) 2 and 40MPa between, 5 and 30MPa between, 7 and 20MPa between, or 10 and 18MPa between.In another embodiment, HPS preferably is higher than 150MPa being higher than operation under the pressure of 138MPa, preferably is higher than 200MPa.

At reactor drum delivery valve place, pressure is reduced to beginning isolating polymer and unreacted monomer, comonomer, and inert material is ethane for example, propane, solvent is hexane for example, toluene etc.Temperature in the separation vessel can remain on the Tc that is higher than polymeric articles when perhaps polymeric articles does not have ctystallizing point (if then be higher than 80 ℃), but pressure can the subcritical point.To such an extent as to pressure only needs enough height monomers, for example propylene can pass through the standard condensed.The logistics of liquid recycled matter can be used the liquid pumping system to replace ultra-compressor of Vilaterm unit needs and be recycled in the reactor drum then.In this reactor drum lower pressure will reduce liquid polymers mutually in monomeric concentration, this can cause lower rate of polymerization.In some embodiments, this rate of polymerization can enough lowly need not be added catalyzer poison or " agent for killing " so that operate this system.Catalyst kill agent (for example stoping the reaction in the high pressure recycling) then must be removed any potential catalyzer poison from the logistics that is rich in propylene monomer of recycling if desired, for example through use ADSORPTION IN A FIXED BED agent or through removing with aluminum alkyls.

Optionally, separation vessel can still operated in the monomer/polymer two phase region under the emergent pressure that be higher than monomer or grams of monomer blend.If high-pressure polyethylene (HPPE) equipment with repacking prepares polymkeric substance, this is a preferable methods economically.Before the suction unit that turns back to second compressor, to the top material cooling and the dewaxing of recycling separation vessel.

Then can be in light pressure separator through another depressurization steps from the polymkeric substance of this separation vessel.To such an extent as to the temperature of this container will remain and be higher than melting point polymer and can be used as liquid from the polymkeric substance of this container and be fed directly in forcing machine or the static mixer.Pressure in this container will keep low value to wait until in condensing surface or the pumping system so that reclaim unreacted monomer through using compressor.

Polymer recovery

Be rich in can directly the delivering to mutually in the coupled devolatilisation system of polymkeric substance, it can comprise placed in-line one or more flash chamber, perhaps light pressure separator (LPS); Each all operation under the successive lower pressure; And the devolatilisation system can comprise as the devolatilisation forcing machine of final step or other and remove the volatile matter device, LIST DTB for example, and it can be from LIST USA Inc.; Of Charlotte, North Carolina obtains.The low pressure separation vessel can adiabatic operation, or the optional interior heater that can have film or fall the bar type.It is sepn process so that from last polymkeric substance, separate remaining volatile matter that this volatile matter removes, and need not take older, invalid method, for example stripping.Last devolatilisation device (forcing machine, LIST DTB etc.) can be operated under strong vacuum, and can choose wantonly and use steam stripping agent for example water or nitrogen, with the volatile content of further reduction polymkeric substance.In case removed volatile matter, product leaves last devolatilisation step and transfers to then in other processes, for example granulation and packing.

Be rich in the effective and economic recycling of monomeric phase

In the preferred embodiment of the invention; Being rich in monomeric phase deals with slightly and just is recycled in the polymerization system to avoid the cost investment in the recirculation device; And avoid comprising heating medium (steam, deep fat, electricity etc.) and heat-eliminating medium (water coolant; The consumption of expensive general facilities salt solution, cooling air etc.).The temperature that is rich in monomeric phase therein in the fluid-liquid separation vessel (for example HPS) is higher than in the embodiment of polymerization system feeding temperature, need be rich in some coolings of monomeric phase.If need not remove anhydrate or other polar contaminants to remain on catalyst productivity economic in the polymerization system, will being rich in monomeric recirculation stream afterwards, to be cooled to the polymerization system feeding temperature can be all needed.Such embodiment comprises and is cooled to-40 to 100 ℃ with being rich in monomeric recirculation stream, or-20 to 90 ℃, or 0 to 90 ℃, or 20 to 90 ℃, or 50 to 90 ℃.Needs remove anhydrate or other polar contaminants to remain in the catalyst productivity economic in the polymerization system; Can on desiccant bed, carry out drying afterwards, and be rich in monomeric recirculation stream must be cooled to the polymerization charge temperature or wherein siccative have acceptable ability with remove anhydrate and/or the temperature of other polar impurities (for example catalyzer poison) than low value.Need in the siccative dry situation this, an embodiment comprises and is cooled to-40 to 80 ℃ with being rich in monomeric recirculation stream, or-20 to 60 ℃, or 0 to 40 ℃, or 20 to 40 ℃.When monomeric recirculation stream is rich in cooling; Be present in the low or very low-molecular-weight polymkeric substance that is rich in the monomeric logistics and can be used as solid precipitation; It can be chosen wantonly through strainer, " pounding out " jar etc. and remove; Perhaps stay in the return logistics, this depends on the Css that low-molecular weight polymer level in requirement of products and the product is divided.

Heat integration

The heating of polymerisation medium therein and being rich in the embodiment of the present invention that the cooling of monomeric recirculation flow all needs; The heat integration interchanger advantageously is installed usually, and it will be defined as any device of heat-shift between the polymerisation medium that leaves the monomeric phase of being rich in of fluid-liquid separator and the reliever upper reaches.Monomeric recirculation stream is rich in this heat exchange while heated polymerizable medium and cooling.Heat exchange therein is not enough to polymerisation medium is brought up to desired temperatures and/or will be rich in the embodiment that monomeric recirculation stream is cooled to desired temperatures, and supplementary heating and cooling system can be used for the heat integration interchanger collaborative.In this embodiment, the heating medium that is preferred for polymerisation medium includes but not limited to steam, thermal oil system and electric heating system.The additional heat-eliminating medium that preferably is used to be rich in monomeric recirculation stream includes but not limited to cooling system of fresh water, brine system, air cooling interchanger and similar system.

Application to two phase-polymerization systems

In another embodiment of the invention; Polymerization system (for example describing among the WO2004/026921) is operated under the pressure that is lower than cloud point pressure; Two phases (fluid-liquid) polymerisation medium directly is transferred in the gravity separation vessel; If the phase that expectation strengthens being rich in polymkeric substance be rich in monomeric being separated mutually, choose the reliever that can further reduce wantonly through pressure wherein.In this embodiment, be rich in monomeric to be recycled to polymerization system with the described identical mode of polymerization system that is used for operation under the pressure on the above-mentioned cloud point pressure.Other aspects of the present invention; Comprise that spinodal decomposes; Be rich in the additional cooling of monomeric recirculation stream; The siccative that is rich in monomeric recirculation stream is dry, the low-molecular weight polymer that from be rich in monomeric recirculation stream, is precipitated out remove and catalyst kill also can be used in this embodiment.

From be rich in monomeric recirculation stream, remove dehydrogenation

Many catalyst systems used herein (for example those disclosed among the WO2004/026921) produce the by product of a spot of hydrogen as polyreaction.In addition, hydrogen can be the reactor feed that is used for polymerization process described herein.Therefore, in the embodiment of the polymerization processes that not in polymerization process, all do not consume of hydrogen, do not have a spot of hydrogen in the polymerisation medium therein, and the major part in these hydrogen can be retained in leave being rich in of fluid-liquid phase separation container (for example HPS) monomeric mutually in.In one embodiment; The amount that is rich in hydrogen in the monomeric recirculation stream is less than the amount of hydrogen in the streams of the merging that joins polymerization process; And in this embodiment; Newly replenishing of hydrogen in the polymerization process material can be reduced so that compensate the hydrogen of this recycling, and need further not handle to remove dehydrogenation being rich in monomeric recirculation stream.In another embodiment; The amount that is rich in hydrogen in the monomeric recirculation stream is more than the total amount of the hydrogen of the streams desired of the merging of polymerization process; And in this embodiment, additional processing steps can be increased in the method that is rich in monomeric phase recycling.This additional processing steps can include but not limited to single step or multistep flash chamber, separation column or hydrogenation bed.The processing that removes dehydrogenation can be applied to all is rich in the monomeric logistics, or hydrogen removes under the situation that requires to allow therein, is applied to the only part or the slip-stream of being rich in the monomer recirculation stream.

Catalyst kill

The use of method disclosed herein has reduced the monomer concentration that is rich in the phase of polymkeric substance with respect to the liquid state of polymerisation medium, its cause conversely being rich in polymkeric substance mutually in low-down post polymerization speed.This rate of polymerization can enough be hanged down to operate this system need not add catalyzer poison or " agent for killing ".Do not kill compound if add, then remove afterwards the step of agent for killing and just can delete.Catalyst kill agent stipulates from the monomeric logistics of being rich in of recycling, to remove any potential catalyzer poison (for example through using desiccant bed or passing through the aluminum alkyls removing) afterwards if desired.Polar material for example water, alcohol or StNa/calcium can be used as agent for killing.If agent for killing has low volatility, the selection of agent for killing and consumption depend on the needs of recycling propylene and comonomer cleaning and product property.

The selection of propylene feed purity

Propylene is purchased acquisition, and it is in 99.5% polymerization-grade purity and two levels of chemical grade purity of about 93 to 95%.The selection of material can be adjusted the material excess dilution of purification level to avoid carrying out through inertia propane from the needs of recycling.

Polymeric articles

Separate and the polymkeric substance that reclaims can have any structure through method of the present invention, comprise block, line style, radial, star, branching and these associating.Some embodiment of the present invention separate and reclaimed have unique microstructures Vestolen PP 7052 and polyacrylic multipolymer.Method of the present invention can be used to prepare novel isotaxy and syndyotactic polymer compsn.In other embodiments, method of the present invention can be used to prepare crystalline polymer.

Some embodiment of disclosed method separate and have reclaimed polymkeric substance, are typically propene polymer, and the fusing point that it had is 70 to 165 ℃, and/or its weight-average molecular weight is 2; 000 to 1,000,000,10,000 to 1; 000,000,15,000 to 500,000,25; 000 to 250,000 or 35,000 to 150,000g/mol.

Embodiments more of the present invention are separated and the polymkeric substance of recovery has 1-30J/g, the melting heat Δ H of 2-20J/g or 3-10J/g _fHeavy in another embodiment, the polymkeric substance that method of the present invention is produced has 110J/g at the most, is preferably 50 to 110J/g and 70 to 100J/g Δ H more preferably _f

In another embodiment; Polymkeric substance isolating and that reclaim here has under 180 ℃ that the Brookfield viscometer measures and is lower than 10; The melt viscosity of 000 centipoise; Perhaps be 1000 to 3000cPs for some embodiments (for example packing and tackiness agent), and for other use preferably 5000 and 10000cP between.

The invention further relates to: 1. method that is used for olefin polymerization; Comprise the steps: that (a) is in dense thick fluid polymerization in homogeneous phase system; In one or more reactor drums; Under the temperature that is higher than the polymerization system Tc and be not less than under following 10MPa of polymerization system cloud point pressure (preferred 1MPa) and the preferred pressure less than 200MPa; Make the olefinic monomer and 1 that exists in 30 weight % or more amount (based on the weight of monomer that gets into reactor drum and comonomer [being 40wt% or more many optionally perhaps]) with three or more a plurality of carbon atoms based on the weight of polymerization system) one or more catalyst compound, 2) one or more acvators, 3) comonomer (preferred 1 to 45mol%) (based on the monomer of entering reactor drum and the amount meter of comonomer [or optionally count 0 and arrive 50wt%]) of 0 to 50 mole of % based on the weight of polymerization system; And 4) 0 to 40wt% (preferred 0 to 25wt%; More preferably 0 to 10wt%) thinner or solvent (based on the weight meter of polymerization system) contact, wherein polymerization system comprises monomer, the comonomer of any existence; Any scavenging agent, the thinner of any existence or solvent and polymeric articles; (b) form the reactor effluent that comprises polymkeric substance-monomer mixture; (c) after it leaves reactor drum and in step (e), reduce the polymkeric substance-monomer mixture of optionally heating (b) before or after the pressure; (d) polymkeric substance-monomer mixture of collection (b) in separation vessel; (e) pressure that comprises the reactor effluent of polymkeric substance-monomer mixture in (b) is reduced to below the cloud point pressure so that in separation vessel, form before or after collected polymer-monomer mixture and comprises the phase that is rich in polymkeric substance and be rich in monomeric two-phase mixture mutually; Wherein reactor drum (if use more than a reactor drum then be at least one reactor drum) if in pressure 7 and the 100MPa of pressure in being higher than independent container between and when the Tc or the polymkeric substance that are higher than polymkeric substance of the temperature in the container do not have Tc separately; This temperature is higher than 80 ℃, and whichever is higher; (f) will be rich in polymkeric substance be rich in monomeric being separated; And (g) be rich in the monomeric one or more reactor drums that are recycled to mutually in (a) isolating; And (h) from be rich in polymkeric substance mutually reclaim polymkeric substance.2. the method for paragraph 1, it further is included in heated polymerizable thing-monomer mixture in the separation vessel (preferably preventing to be rich in the phase crystallization of polymkeric substance) or is connected to the step of heated polymerizable thing (preferably preventing to be rich in the phase crystallization of polymkeric substance) in the indirect heating loop of separation vessel at fluid.3. paragraph 1 or 2 method, wherein before reducing pressure, the polymkeric substance-monomer mixture of collection is under the pressure that is higher than cloud point pressure and is higher than under the temperature of Tc of polymkeric substance-monomer mixture in step (d).4. paragraph 1,2 or 3 method, its further comprise from be rich in polymkeric substance mutually separate volatile matter step.5. paragraph 1,2,3 or 4 method, and it further comprises being rich in being fed to mutually in the coupled devolatilization sundries so that from polymkeric substance, separate the step of volatile matter of polymkeric substance.6. the method for paragraph 5, wherein coupled devolatilization sundries turn round under rough vacuum, make to be rich in being flashed to mutually in the devolatilization sundries of polymkeric substance.7. paragraph 5 or 6 method, wherein coupled devolatilization sundries are the devolatilisation forcing machine.8. paragraph 1,2,3,4,5,6 or 7 method, wherein separating step (f) the cloud point that is lower than polymerization system be higher than (f) in be rich under the Tc mutually of polymkeric substance and carry out.9. the method for paragraph 8, wherein separation vessel is a gravity separation vessel.10. each method of paragraph 1 to 9; It further comprises from recycling step (g) isolating and is rich in the monomeric low-molecular weight polymer of removing in mutually (for example less than the weight-average molecular weight (Mw) of 10000g/mol; Preferably less than 5000g/mol, preferably less than 1000g/mol).11. the method for paragraph 10, wherein low-molecular weight polymer is removed through using at least one to pound out jar.12. each method of paragraph 1 to 11, wherein olefinic monomer is present in the polymerization system preferred 75 weight % or more with 55 weight % or more amount.13. each method of paragraph 1 to 12, wherein the pressure of polymerization system is less than about 140MPa, preferably 15 and 140MPa between, preferably 15 and 50MPa between.14. each method of paragraph 1 to 13, wherein temperature is between 60 and 180 ℃, preferably between 85 and 180 ℃, preferably between 95 and 180 ℃, preferably between 100 and 180 ℃.15. each method of paragraph 1 to 14 wherein is rich in monomeric comprising mutually less than the about low-molecular weight polymer of 0.1wt%.16. each method of paragraph 1 to 15 wherein is rich in monomeric about 0.3 to about 0.4 gram/mL the density that has mutually.17. each method of paragraph 1 to 16, what wherein be rich in polymkeric substance has about 0.6 to about 0.7 gram/mL density mutually.18. each method of paragraph 1 to 17, wherein in the step (e), pressure descends with at least about speed of 2MPa/sec; Be preferably 3MPa/sec at least, be preferably 4MPa/sec at least, be preferably 5MPa/sec at least; Be preferably 6MPa/sec at least, be preferably 7MPa/sec at least.19. each method of paragraph 1 to 18, wherein step (a) is carried out in mutually in single liquid state.20. the method for paragraph 19, wherein the temperature and pressure of polymerization system remains on the value that is higher than fluid-solid phase transition temperature and pressure.21. each method of paragraph 1 to 18, wherein step (a) is carried out in two phase liquid-liquid systems.22. the method for paragraph 21, wherein the temperature of polymerization system remains below cloud point temperature and the value that is higher than the fluid-solid phase transition temperature of polymerization system.23. each method of paragraph 1-22, wherein solvent and/or thinner are present in the polymerization system with the amount that is less than 10wt%, preferably are less than 1wt%.24. each method of paragraph 1 to 23, the olefinic monomer that wherein has three or more a plurality of carbon atoms comprises propylene.25. each method of paragraph 1 to 24, wherein polymerization system comprises the propylene monomer of 55-100wt%, 0 to 45wt% copolymerized monomer mixture, and said copolymerized monomer mixture comprises at least a ethene that is selected from; Butylene, hexene, octene, decene; Dodecylene, 4-methyl-1-pentene, Dicyclopentadiene (DCPD), norbornylene; The terminal olefin of C4-C2000, the α of C4-C2000, the α of interior-diolefine and C4-C2000, the comonomer of ω-diolefine; Optimal ethylene, butylene, one or more in hexene or the octene.26. each method of paragraph 1 to 25, wherein catalyst compound is expressed as following formula:

M wherein ¹Be selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten (preferred zirconium and hafnium); R ¹And R ²Identical or different, and be selected from Wasserstoffatoms, C ₁-C ₁₀Alkyl, C ₁-C ₁₀Alkoxyl group, C ₆-C ₁₀Aryl, C ₆-C ₁₀Aryloxy, C ₂-C ₁₀Thiazolinyl, C ₂-C ₄₀Thiazolinyl, C ₇-C ₄₀Aralkyl, C ₇-C ₄₀Alkaryl, C ₈-C ₄₀Arylalkenyl, OH group or halogen atom; Or the optional alkyl of using, (the preferred R of one or more the substituted conjugated dienes in three (alkyl) silyls or alkyl three (alkyl) the silyl alkyl ¹And R ²Be alkyl, for example methyl or ethyl, or be the halogen root, for example chlorine root); R ³-R ¹²Identical or different, and be selected from Wasserstoffatoms, halogen atom, C ₁-C ₁₀Halogenated or not halogenated alkyl, C ₆-C ₁₀Halogenated or not halogenated aryl, C ₂-C ₁₀Halogenated or not halogenated thiazolinyl, C ₇-C ₄₀Halogenated or not halogenated aralkyl, C ₇-C ₄₀Halogenated or not halogenated alkaryl, C ₈-C ₄₀Halogenated or not halogenated arylalkenyl ,-NR ' ₂,-SR ' ,-OR ' ,-OSiR ' ₃Or-PR ' ₂Group, wherein R ' is a halogen atom, C ₁-C ₁₀Alkyl or C ₆-C ₁₀One of aryl; Perhaps R ⁵To R ⁷In the group of two or more vicinities can form one or more rings (preferred R with the atom that connects them ³Be methyl, ethyl or butyl), and adjacent R ¹¹And R ¹²Can form one or more saturated rings or aromatic ring (preferred R ¹¹And R ¹²Merge to form substituted or unsubstituted naphthyl with phenyl ring), R ¹³Be selected from:

-B (R ¹⁴)-,-Al (R ¹⁴)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO ₂-,-N (R ¹⁴)-,-CO-,-P (R ¹⁴)-,-P (O) (R ¹⁴)-,-B (NR ¹⁴R ¹⁵)-with-B [N (SiR ¹⁴R ¹⁵R ¹⁶) ₂]-, R ¹⁴, R ¹⁵And R ¹⁶Separate hydrogen, halogen, the C of being selected from ₁-C ₂₀Alkyl, C ₆-C ₃₀Aryl, C ₁-C ₂₀Alkoxyl group, C ₂-C ₂₀Thiazolinyl, C ₇-C ₄₀Aralkyl, C ₈-C ₄₀Arylalkenyl and C ₇-C ₄₀Alkaryl, perhaps R ¹⁴And R ¹⁵Atom with connecting them forms ring; And M ³Be selected from carbon, silicon, germanium and tin, perhaps R ¹³Represent with following formula:

R wherein ¹⁷To R ²⁴With R ¹And R ²Definition identical, perhaps R ¹⁷To R ²⁴In two or more adjacent groups with, comprise R ²⁰And R ²¹, the atom that connects them forms one or more rings, M together ²Be carbon, silicon, germanium or tin (preferred R ¹³Be dimetylsilyl or diphenylmethyl siloyl group).27. each method of paragraph 1 to 26; Wherein acvator is selected from aikyiaiurnirsoxan beta (preferable methyl aikyiaiurnirsoxan beta) and non-coordination anion (preferred trimethyl ammonium four (pentafluorophenyl group) borate; N, accelerine four (pentafluorophenyl group) borate, triphenylcarbenium four (pentafluorophenyl group) borate; Or N, accelerine four (perfluorophenyl) borate).28. each method of paragraph 1 to 27 is monomericly removed hydrogen and excessive catalyst kill agent mutually from being rich in before wherein being recycled in one or more polymerization reactors.29. each method of paragraph 1 to 28 wherein is rich in monomeric phase and differs 0.2g/mL at least with the phase density that is rich in polymkeric substance.30. each method of paragraph 1 to 29, wherein polymerization system is single-phase supercutical fluid.31. each method of paragraph 1 to 30, wherein the residence time in the separation vessel is 1 minute to 30 minutes, is preferably 1 to 15 minute.

All Files described herein is all incorporated the present invention into through reference paper, with on the inconsistent degree of this paper does not comprise any priority document and/or test process at them.Because with the general description in front and special embodiment explanation and the form of describing of the present invention is conspicuous, can carries out different improvement and do not deviate from the spirit and scope of the present invention.Therefore, this and do not mean that the present invention limits through them.Same,, think " comprising " speech and " comprising " speech synonym based on the purpose of Australian law.

Claims (25)

1. a method that is used for olefin polymerization comprises the steps:

(a) in the single-phase supercritical polymerization system of dense thick fluid homogeneous phase; In one or more reactor drums; Under the temperature that is higher than the polymerization system Tc and be not less than under the pressure of the following 10MPa of polymerization system cloud point pressure, make weight meter based on monomer that gets into reactor drum and comonomer with 30 weight % or more measure the olefinic monomer and 1 that exists with three or more a plurality of carbon atoms) one or more catalyst compound, 2) one or more acvators; 3) based on the comonomer of 0 to 50 mole of % of amount meter of monomer that gets into reactor drum and comonomer; And 4) based on the thinner or the solvent contact of the weight meter of polymerization system 0 to 40wt%, wherein polymerization system comprises monomer, the comonomer of any existence; Any scavenging agent, the thinner of any existence or solvent and polymeric articles;

(b) form the reactor effluent that comprises polymkeric substance-monomer mixture;

(c) after it leaves reactor drum and in step (e), reduce the polymkeric substance-monomer mixture of optionally heating (b) before or after the pressure;

(d) under the pressure that is higher than cloud point pressure and be higher than polymkeric substance-monomer mixture of in separation vessel, collecting (b) under the temperature of Tc of polymkeric substance-monomer mixture;

(e) pressure that under the speed of 2MPa/sec at least, comprises the reactor effluent of polymkeric substance-monomer mixture in (b) forms two-phase mixture before or after being reduced to below the cloud point pressure with collected polymer-monomer mixture in separation vessel; It comprises the phase that is rich in polymkeric substance be rich in mutually monomeric; Wherein be rich in monomeric phase and differ 0.2g/mL at least with the density mutually that is rich in polymkeric substance; Reactor drum wherein; If use more than a reactor drum then be at least one reactor drum; If in pressure 7 and the 100MPa of pressure in being higher than separation vessel between with separation vessel wherein in pressure when preventing to be rich in Tc that monomeric all or part of evaporation and the temperature in the separation vessel mutually be higher than polymkeric substance or polymkeric substance and not having Tc, this temperature is higher than 80 ℃, whichever is higher;

(f) through wherein carry out isolating gravity settling the cloud point that is lower than polymerization system be higher than the Tc mutually that is rich in polymkeric substance under will be rich in polymkeric substance lack 30% unreacted monomeric monomeric being separated of being rich in comprising than the elute as many as; And

(g) be rich in the monomeric one or more reactor drums that are recycled to mutually in (a) isolating; And

(h) from be rich in polymkeric substance mutually reclaim polymkeric substance.

2. the method for claim 1, it further is included in heated polymerizable thing-monomer mixture in the separation vessel or is communicated to the step of heated polymerizable thing in the indirect heating loop of separation vessel at fluid.

3. the method for claim 1, its further comprise from be rich in polymkeric substance mutually separate volatile matter step.

4. the method for claim 1, it further comprises being rich in being fed to mutually in the coupled devolatilization sundries so that from polymkeric substance, separate the step of volatile matter of polymkeric substance.

5. the method for claim 4, wherein coupled devolatilization sundries turn round under rough vacuum, make to be rich in being flashed to mutually in the devolatilization sundries of polymkeric substance.

6. the method for claim 4, wherein coupled devolatilization sundries are the devolatilisation forcing machine.

7. the process of claim 1 wherein that separation vessel is a gravity separation vessel.

8. the method for claim 1, it further comprises being rich in from recycling step (g) isolating monomericly removes the step that has less than the polymkeric substance of 10000g/mol weight-average molecular weight (Mw) in mutually.

9. the method for claim 8, wherein low-molecular weight polymer jar is removed through using at least one to pound out.

10. the process of claim 1 wherein that olefinic monomer is present in the polymerization system with 55 weight % or more amount.

11. the process of claim 1 wherein that the pressure of polymerization system is less than 140MPa.

12. the process of claim 1 wherein and be rich in the monomeric density that has 0.3 to 0.4 gram/mL mutually.

13. the process of claim 1 wherein the density that has 0.6 to 0.7 gram/mL mutually that is rich in polymkeric substance.

14. the step of the process of claim 1 wherein (a) is carried out in mutually in single liquid state.

15. the method for claim 14, wherein the temperature and pressure of polymerization system remains on the value that is higher than fluid-solid phase transition temperature and pressure.

16. the process of claim 1 wherein that solvent and/or thinner are present in the polymerization system with the amount that is less than 10wt%.

17. the process of claim 1 wherein that the olefinic monomer with three or more a plurality of carbon atoms comprises propylene.

18. the process of claim 1 wherein that polymerization system comprises the propylene monomer of 55-100wt%, 0 to 45wt% copolymerized monomer mixture, said copolymerized monomer mixture comprises at least a ethene that is selected from; Butylene, hexene, octene, decene; Dodecylene, Dicyclopentadiene (DCPD), norbornylene, the terminal olefin of C4-C2000; The α of C4-C2000, the α of interior-diolefine and C4-C2000, the comonomer of ω-diolefine.

19. the method for claim 18, wherein the terminal olefin of C4-C2000 is a 4-methyl-1-pentene.

20. the method for claim 18, wherein comonomer is an ethene, butylene, one or more in hexene or the octene.

21. the process of claim 1 wherein and hydrogen and excessive catalyst kill agent are monomericly removed mutually from being rich in before being recycled in one or more polymerization reactors.

22. the process of claim 1 wherein that being rich in monomeric phase differs 0.5g/mL at least with the phase density that is rich in polymkeric substance.

23. the process of claim 1 wherein that the residence time in the separation vessel is 1 minute to 30 minutes.

24. the process of claim 1 wherein that this method carries out in tubular reactor or autoclave reactor.

25. the process of claim 1 wherein that this is the continuation method of in tubular reactor or autoclave reactor, carrying out.

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